Silyated addition polymers with pendant ionic moieties

ABSTRACT

Addition interpolymers with pendant ionic moieties and pendant reactable silane moieties are prepared by addition polymerization of ethylenically unsaturated monomers having ionic moieties with organofunctional silane compounds having ethylenic unsaturation in the organofunctional moiety of the silane where the silane also has reactable alkoxy and/or hydroxy group. The addition polymerization is performed in the presence of a free radical initiator at an elevated temperature up to around 90° C. and in a nonoxidizing atmosphere. The amount of the ionic monomer is effective to result in the interpolymer having at least water dispersibility and most suitably water emulsifiability and the amount of the silane monomer is in the range of about 1 to about 15 weight percent of the interpolymer. The interpolymer may be prepared with one or more additional ethylenically unsaturated monomers where the amount does not decrease the ionic character of the interpolymer below that which renders the interpolymer water emulsifiable.

This is a division of application Ser. No. 07/292,859, filed Jan. 3,1989 now U.S. Pat. No. 4,983,699.

The present invention is directed to addition polymeric materials havingpendant reactable silylation and having at least one pendant ionicmoiety or group.

BACKGROUND OF THE INVENTION

Vinyl polymers with ionic groups such as sulphonates or quaternaryammonium salts have found applications in various fields. Since thesepolymeric materials are water soluble, their utilization as films orcoatings on inorganic oxide surfaces and substrates results in a lesstenacious film or coating that is not water fast. A moist environment isanathema to such films and coatings on inorganic oxide surfaces becauseof their ease of removal under such conditions. What is desired in theart is a more tenacious film or coating of a polymeric material withionic functional moieties so that better adhesive affinity spawns newuses for these polymeric materials on inorganic oxide surfaces.

It is an object of the present invention to provide polymeric materialshaving at least one ionic moiety and also having good affiliation withinorganic oxide surfaces.

SUMMARY OF THE INVENTION

The aforementioned object and other objects gleaned from the followingdisclosure are accomplished by the present invention. The inventioncomprises polymeric reaction product of at least one ethylenicallyunsaturated monomer having an ionic moiety (ionic-containing monomer)and a copolymerizable organo-functional, alkoxy/hydroxy, silanecompound. The silane compound has ethylenic unsaturation forcopolymerization in its organofunctional moiety and has from around 1 to3 alkoxy and/or hydroxy groups associated with the silane (silanecompound). The amount of the ionic-containing monomer is effective toyield enough pendant ionic groups in the resulting polymer to providefor at least its emulsifiability in water. The amount of the silanecompound is an effective amount to yield pendant hydrolyzable silanegroups for the polymer in an amount of about 1 to about 15 weightpercent of the polymer. The polymeric reaction product is produced fromat least these two monomers or with the addition of one or moreethylenically unsaturated monomers by addition polymerization. Thispolymerization includes: the presence of a free radical initiationcatalyst in an effective catalytic amount, the presence of a liquidcarrier, a temperature of polymerization greater than room temperature,and a nonoxidizing atmosphere. When the ionic monomer and ethylenicallyunsaturated silane compound are the only monomers used in preparing thepolymer, the ionic monomer is typically present in a predominant amountin the range of around 85 to 99 weight percent. When additionalethylenically unsaturated monomer is present in addition to the twopreviously mentioned monomers, the ionic monomer is present in theamount of around 10 to around 98 weight percent of polymer.

Inorganic and organic surfaces or substrates which have reactablehydroxyl functionality can be treated with the interaction polymer ofthe present invention with or without a carrier. Also, the interactionpolymer can be cured to form a film on the surfaces or substrates byhaving a curing agent added to a formulation of the interaction polymeror by evaporating the carrier or by drying in contact with air or anyart recognized method.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENT

The curable addition polymeric material of the present invention withpendant ionic moieties and pendant hydrolyzed or hydrolyzable silanemoieties has one or more repeating units from an ethylenicallyunsaturated monomer having an ionic moiety and from ethylenicallyunsaturated monomer having alkoxy and/or hydroxy silane moiety. Theethylenically unsaturated monomer to which the ionic moiety is bondedcan be any ethylenically unsaturated monomer having at least one

    (CH.sub.2 ═CH) or (HC═CH)

group. Nonexclusive examples of suitable ethylenically unsaturatedmonomers include:

a) substituted and unsubstituted acrylate and methacrylate compoundsincluding: the alkyl acrylates such as methyl acrylate, ethyl acrylate,butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, and the like;the alkyl methacrylates such as methyl methacrylate, butyl methacrylate,2-ethylhexyl methacrylate, lauryl methacrylate, and the like; and

b) methyl alpha-chloracrylate; hydroxyethyl acrylate;dihydroperfluorobutyl acrylate; propylacrylate; isobornyl acrylate;cyclohexyl acrylate; dodecyl acrylate; hexyldecyl acrylate; isopropylacrylate; tetradecyl acrylate; ethylene glycol; sec butyl acrylate;dimethacrylate; methacrylate; 2-n-tert-butylaminoethyl methacrylate;2-butyl methacrylate; glycidyl methacrylate; 2 chloroethyl methacrylate;3,3-dimethylbutyl methacrylate; 2 ethylhexyl methacrylate; 2methoxyethyl methacrylate; pentyl methacrylate; methyl methacrylate;ethyl methacrylate; n-butyl methacrylate; isobutyl methacrylate; sodiummethacrylate; isopropyl methacrylate; propyl methacrylate and the like;and

c) unsaturated nitriles such as acrylonitrile, methacrylonitrile andethacrylonitrile. Still other unsaturated monomers which can be usedinclude vinyl aromatic hydrocarbons such as acrolein, styrene,alpha-methyl styrene. Typical substituted styrene compounds include:alpha methyl; styrene, vinyltoluene; modified styrene; 4-bromostyrene;4-chloro-3-fluorostyrene; 2-chlorostyrene; 2,5-dichlorostyrene;2,3-difluorostyrene; 2,4-dimethyl styrene; 4-ethoxystyrene;4-ethylstyrene; 4-hexadecylstyrene; 3-hydroxymethylstyrene;4-iodostyrene; 4-isopentoxystyrene; 4-nonadecylstyrene, and the like,and vinyltoluene, vinyl acetate, vinyl chloride and the like and epoxyfunctional monomers such as glycidyl methacrylate and the like.

Nonexclusive examples of the ionic moieties include: sulfonates,quaternary ammonium salts, and carboxylate groups, and these may have anassociation with the aforelisted ethylenically unsaturated monomers byany method known to those skilled in the art. For instance, thesulfonation of the monomer materials to produce sulfonates may occur bytreatment of alpha-olefins with SO₃ or through the reaction of aromatichydrocarbons with arylhalide sulfonates in the presence of thionylchloride. Another method is the reaction of unsaturated hydrocarbonswith metal sulfites or bisulfites to form metal sulfonates (sulfitationor bisulfitation) or from sulfonating 2-bromoethylbenzene followed bytreatment with alkali to effect dehydrobromonation and formation of thesulfonite salt.

Nonexclusive examples of the quaternary ammonium salt moieties of thepresent invention are those having the formula: ##STR1## in which,broadly, R₁, R₂, R₃ and R₄ are organic groups, three of the four may beany monovalent organic radical, or two of them taken together may be adivalent organic group, or the compounds can be cyclic and the nitrogenatom can be included in a heterocyclic ring. The moiety X⁻ may bechlorine, bromine, fluorine, alkoxy, nitro, aryloxy and carboxy groupsand the like. Nonexclusive examples of the quaternary ammonium groupsare: pyridinium, piperidinium, pyrrolidinium, and quinolinium ions. Oneof the valences R₁, R₂, R₃ or R₄ is an unsaturated group such as thefollowing: alkyl acrylates, the alkyl group having one to eight carbonatoms, e.g., methyl acrylate, ethyl acrylate, etc., preferably ethylacrylate, and ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,octenyl, nonenyl, decenyl, hendecenyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,nonadecenyl, and eicosenyl. While, as indicated, the nitrogensubstituents can be any organic groups, for three of the four it ispreferred that the nitrogen valences represented by R₁, R₂, R₃ and R₄,be satisfied by unsubstituted hydrocarbon groups of from 1 to 20 carbonatoms and/or polyoxyalkylenes like polyoxyethylenes and polyoxymethyleneand mixture of any of these. The substituents can be the same ordifferent, and if a divalent group is used, it will satisfy two of thevalences. Nonexclusive examples of unsubstituted hydrocarbon radicalsinclude such aliphatic groups as methyl, hendecyl, ethyl, dodecyl,propyl, tridecyl, butyl, tetradecyl, pentyl, pentadecyl, hexyl,hexadecyl, heptyl, heptadecyl, octyl, octadecyl, nonyl, nonadecyl,decyl, and eicosyl. It will be understood that the substituents or anyof these can be cyclic and, for instance, they can be alicyclic. Thus,as an example a substituent of hexyl includes the cyclohexyl group.Similarly, the cycloalicyclic compounds can be unsaturated and they canbe unsaturated in varying degrees. There can be used, for instance, the1,3-cyclohexyldienyl group. In addition to the aliphatic andcycloaliphatic substituents of the character described, one can usearomatic types of substituents in one of the positions of R₁, R₂, R₃ andR₄. For instance, one can use phenyl; abietyl; naphthyl; fluoryl; anddiphenyl.

While, as has been indicated, it is preferred to satisfy the valencesR₁, R₂, R₃ and R₄ with unsubstituted hydrocarbon groups of from one totwenty carbon atoms and/or polyoxyalkylene, one can prepare compounds ofthe invention by using substituted hydrocarbon groups. It seems hardlynecessary to list all of the possible substitutions since such compoundsare generally well known as applied to quaternary ammonium salts andsince the invention is here not directed primarily to the cation of themolecule.

In employing the above-described substituents one skilled in the artwill not attempt to put too many long-chain substituents on the nitrogenatom because of the well-known phenomenon of stearic hindrance. Also,the carboxylate moiety can be derived from an ethylenically unsaturatedmonomer that is an acid monomer selected from the group consisting ofacrylic acid, methacrylic acid, fumaric acid, maleic acid, maleicanhydride and itaconic acid. The preferred acid comonomer is acrylicacid. The carboxylic acid groups on the ethylenically unsaturatedmonomer can convert to ionic moieties through neutralization of themonomer or subsequent polymeric material.

The amounts of the ionic monomer present in the resulting polymericmaterial are sufficient to provide enough of the pendant ionic group toat least emulsify the polymer in water. Preferably the amount of thependant ionic groups is sufficient to solubilize the polymer in water.Generally the amount of the ionic monomer present in the resultingpolymeric material when only two monomers, the ionic monomer and thesilane monomer, are present is in the range of about 85 to about 95weight percent of the polymeric material.

The preferred ionic monomer is sodium styrene sulfonate for producing asulfonate ionic moiety, and this material is available from E. I. duPontDemours & Company under the designation (SSS). The SSS is a reactivevinyl monomer with a strongly anionic sulfonate group in the form of afree flowing white powder with a 20.5 weight percent solubility in waterat 25° C. having 89 weight percent of the SSS monomer as a minimum andan amount of water of 2.4 weight percent as maximum. Another example ofa sulfonate ionic monomer is 2-acrylamido-2-methyl propanesulfonic acidavailable from Lubrizol Corporation, Wickliffe, Ohio 44092, under thetrade designation AMPS in the form a gray/white crystalline solid havingless than 1 percent volatiles. An example of a quaternary ammonium saltionic monomer that can be used is the quaternized product ofdimethylaminoethyl methacrylate and methyl chloride, which is availableunder the trade designation Sipomer Q-6-75 as a 75 percent activematerial in water from Alcolac, Inc., Baltimore, Md. 21226.

The other component of the addition polymeric material is the organoalkoxysilane compound. The preferred organoalkoxysilane compounds arethe acrylatoalkylalkoxysilanes, such asgamma-acryloxypropyltrimethoxysilane, and the like and themethacrylatoalkylalkoxysilane such asgamma-methacryloxypropyltrimethoxysilane,gamma-methacryloxypropyltriethoxysilane,gamma-methacryloxypropyltris(2-ethoxyethoxy)silane and the like. Ofthese alkoxysilanes, gamma-methacryloxypropyltrimethoxysilane isespecially preferred due to its greater reactivity. Vinylorganoalkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilaneand vinyl tris(2-methoxyethoxy)silane are less effective than theacrylatoalkylalkoxysilanes or methacrylatoalkylalkoxysilanes, but thesemay be used in some instances. Thegamma-methacryloxypropyltrimethoxysilane is available from Union CarbideCorporation under the trade designation A-174 Silane. These organoalkoxysilane compounds can be used in unhydrolyzed, partially hydrolyzed, orfully hydrolyzed form. In the latter two forms, and particularly in thelatter form, precautions should be taken to prevent silane dimerizationand oligomerization through siloxane bonds. Any method for this known tothose skilled in the art can be used such as careful pH control orcapping of the hydroxyl groups to retard siloxane reactions. The amountof the silane compound used in the preparation of the addition polymericmaterial is an effective amount to give a quantity of the pendenthydrolyzed or hydrolyzable silane moieties in the range of around 1 toabout 15 weight percent of the polymeric material. Preferably the amountof the silane is less than around 5 weight percent of the polymericmaterial and most preferably around less than 2 weight percent. Withincreasing percentages of the pendant silane the film formed from thepolymeric material has increasing brittleness. In using the vinylsilanes the activity ratio is lower than that of the acryloxysilanes sothat the order of addition of the silane to the ionic monomer isperformed to disfavor the formation of homopolymer from the ionicmonomer.

In addition to the two aforelisted monomers used in preparing theaddition polymeric material, one or more additional monomers can be usedthat are any ethylenically unsaturated monomer having at least one

    (CH.sub.2 ═CH) or (HC═CH)

group which is preferably devoid of monomers having active hydrogenslike those in hydroxyl, carboxyl or unsubstituted amide groups. Any ofthe aforementioned ethylenically unsaturated monomers useful inpreparing the ionic monomers can be used. It is preferred to use thesame ethylenically unsaturated monomer as the additional monomer andalso as the base monomer for the ionic monomer. When the additionalmonomer is present, it is present in an amount in the range of less thanabout 70 weight percent of the resulting polymeric material. A preferredadditional monomer is methacrylic acid. Its preferred amount in thepolymeric material is an amount that does not terminate the pendantionic character of the polymeric material below that needed for wateremulsifiability and most preferably water solubility. With the use ofone additional monomer the polymeric material that is produced is aterpolymer.

The addition polymeric material, which can be referred to as aninterpolymer or interaction polymer, is prepared, for example, bysolution polymerization of the ionic monomer and the silane monomer inthe presence of a free radical initiator. The solvent is preferablywater but an organic cosolvent having a boiling point not substantiallyin excess of about 100° to 110° C. can be used. A few suitable examplesinclude ethylacetate, toluene, benzene, methyl ethyl ketone or the like.Preferably the organic cosolvent is one that is soluble in water such asacetone. The solution may also include isopropanol which can act as asolvent and a stabilizing agent to thwart undesired gelation. Also, thesolution polymerization is carried out to retard dimerization oroligomerization of the hydrolyzable or hydrolyzed silanes to siloxanematerial. An example of such a procedure is to conduct the reaction in anonoxidizing atmosphere such as with a nitrogen blanket or purge. Afterthe ionic monomer and silane monomer are combined in the solvent and/orcosolvent/solvent combination, the solution is stirred and swept withnitrogen and the temperature of the solution is raised to around 80° C.A catalytic amount of a free radical initiator is added, and thenitrogen flow is continued. Suitable free radical initiators are watermiscible or soluble like alkali metal persulfates. The exothermicpolymerization reaction proceeds with vigorous refluxing and thetemperature can rise to about 80° to 90° C. With subsidence of theexothermic polymerization, stirring and heating to maintain thetemperature at around 80° C. continues for several hours to assuresubstantially complete polymerization. Other polymerization proceduressuch as emulsion polymerization and other free radical polymerizationtechniques known to those skilled in the art can be used.

After formation of the addition interpolymer other materials can beadded to the formulation. An example of these include: a cureaccelerating catalyst such as an organic acid; for example, toluenesulfonic acid, N-butyl phosphoric acid and the like or a metallic saltof an organic acid; for example, tin naphthenate, tin benzoate, tinoctoate, and the like. When an accelerating catalyst is used, it ispresent in an amount of around 0.1 to about 5 weight percent of thetotal formulation.

In preparing the addition interaction polymer, intimate contacting ofthe monomers occurs at a pH less than or equal to around 4 or greaterthan or equal to around 9. The temperature of the reaction is preferablyan elevated temperature of 100° C. or less and most preferably atemperature of around greater than ambient to around 90° C. at ambientpressure. Subatmospheric or superatmospheric pressures can also be usedwith adequate compensation of the temperature for the reaction. Constantagitation accompanies intimate mixing of the monomers, and thecontacting is performed in any manner but preferably the silane monomeris added dropwise to the ionic monomer present in the solvent orsolvent-cosolvent mixture.

The addition interpolymer produced has both pendant ionic moieties andpendant hydrolyzable or hydrolyzed or partially hydrolyzed silanemoieties. The interpolymer can be a copolymer either block or randomdepending on appropriate control of the copolymer reaction, when theionic monomer and silane monomer are the reactants, or a terpolymer whenthese reactants are used with the additional monomer. Any conditionsknown to those skilled in the art can be used to control the copolymerreaction to produce random, block or graft copolymers. When only theionic monomer and silane monomer are used to form the additioninterpolymer, the interpolymer has the formula: ##STR2## where:

R is hydrogen or an alkyl group, and

R' is an organic moiety that in addition with the ##STR3## moiety andionic moiety comprised the ethylenically unsaturated monomer having anionic moiety before addition polymerization;

R" is hydrogen or an alkyl group having one to 5 carbon atoms;

R'" is a (C(O))--O--(CH₂)_(x)) or a (CH₂)_(x) moiety, where x is aninteger from 1 to 6; and R^(IV) is hydrogen and/or an alkyl group having1 to about 4 carbon atoms,

p and q are integers with values of around 80 to around 90 for p andaround 1 to around 20 for q,

x is an ionic group of sulfonate, quaternary ammonium salt orcarboxylate.

When additional monomers are used, their repeating units can be made tooccur randomly throughout the polymer or in blocked fashion in thepolymer. The general molecular weight range of the addition interactionpolymer can range from around that for a dimer to that which is not toohigh to result in a viscosity resulting in gelation or in an inabilityfor application of the interpolymer to a surface. Preferably, theminimum molecular weight is that which is effective to result information of a self-supporting film of the polymer when it is applied toa surface and volatiles are removed.

The formulation of the addition interpolymer with its carrier can beapplied to substrates to form a film or coating by any method known tothose skilled in the art to myriad types of substrates. For instance,useful application techniques include: brushing, dipping, spraying andflow or roll coating and like techniques. The coating can interact withthe substrate by covalent bonding, ionic bonding, hydrogen bonding,and/or Van der Waal bonding through the siliconate anion for the basicsolution or the silanol groups of the interaction polymer. Hydrolyzationis accomplished by increasing the pH of the aqueous solution prior to orduring application to the substrate. Nonexclusive examples of suchsubstrates include: leather, wood, paper of fabric stock, clay coatedprint sheet stock, plastics, inorganic oxides such as glass, aluminum,and steel, and any other inorganic or organic solid material whichpossess either oxygen, chemisorbed or covalently bonded, or hydroxyl(boned or free) at the substrate's initial or exposed surface andincludes any materials which can be treated by coupling agents known inthe prior art. The inorganic oxide material can be in any form includingparticles of regular or irregular shape such as spherical, individualfibers such as glass fibers, woven fiber mats or fabric ceramic fibersor continuous surfaces such as sheets, films, slabs and formed shapes.Specific illustrations of suitably employed inorganic oxide materialsare, for example, brass (with an oxidized surface), aluminum metal(oxidized at its surface), iron or steel (oxidized at its surface),alumina, aluminum trihydrate, siliceous materials such as fume silica,hydrated silica (precipitated silica), silica aerogels, silica xerogels,aluminum silicates, calcium, magnesium silicates, asbestos, glassfibers, silica fibers, clays, molecular sieves, wollastonite, calciumcarbonate, carbon black (including lamp black) titanium dioxide(including titanium dioxide which contains hydrochloric soluble aluminaand/or silica, calcium sulfate, magnesium sulfate, calcium carbonatecontaining a silica coating or agglomerated to silica and the like.

The addition interpolymer of the present invention, which is a polymericadhesion promoter, can be used in essentially the same manner ascoupling agents known in the prior art. It is believed without limitingthe invention that the functional mechanism of the interpolymerapplication with inorganic oxide surfaces is similar to the prior artmonomeric coupling agents. The interpolymer can be supplied to thesurface of the inorganic oxide or organic material prior to contactingwith any additional polymeric materials to be reinforced or augmentedwith the inorganic oxide or organic material. Also, the coatingcomposition can be applied as a primer coating to the surface ofinorganic oxides in the form of the aqueous emulsion.

Once the interaction polymer is applied, usually in an aqueous mixture,curing occurs through drying at ambient or elevated temperatures. Thedrying reduces the moisture content, removes volatiles and possiblyinduces some crosslinking. Lower elevated temperature curing issatisfactory for the interaction compositions of this present invention.The use of ambient temperature curing requires a cure period of up totwo days to achieve a coating with fully developed properties. It shouldbe noted, though, when cured at ambient temperatures, the coating is dryto the touch after only a few hours. A more fully developed cure in thecoating can be achieved by applying heat, with a temperature of lessthan about 150° C. being sufficient.

It is believed, but the invention is not limited by this belief, that inthe cure by drying of the aqueous solution on a substrate improvedadhesiveness of the coating to a substrate is achieved by the silanolbonding to the hydroxyl-containing surface alone or along with a minordegree of siloxane crosslinking of the silylated polyhydroxylatedpolymer.

One particularly useful inorganic oxide surface for the interpolymer isglass fibers; suitable examples of glass fibers include: "E-Glass" or"621-" glass fibers and low or free boron or fluorine derivativesthereof. The interpolymer in an aqueous treating composition is appliedto the fibers, preferably in the fiber forming operation.

In the preferred embodiment of the present invention the ionic monomerdepends somewhat on the desired ionic character, i.e. whether cationicor anionic moieties are desired for the addition interpolymer. When theanionic character is desired, the preferred ionic monomer is the styrenesodium sulfate, and when the cationic character is desired, thepreferred ionic monomer is the quaternary ammonium monomer which ispreferably the Sipomer cationic methacrylate monomer. One of thesemonomers is diluted with distilled water and intimately contacted withgamma-methacryloxypropyltrimethoxy- silane in an effective amount toproduce around less than 5 weight percent pendant reactable silane onthe addition interpolymer and most preferably less than around 2 weightpercent. An additional ethylenically unsaturated monomer may be used ifmaximum ionic character in the addition interpolymer is not desired anda reduction in cost is a concern. The intimate contacting of themonomers is performed in the presence of a free radical initiatorpreferably potassium persulfate in an amount less than around 1 weightpercent in the presence of distilled water as a carrier or solvent. Thereaction is conducted in a suitable vessel for stirring of the materialsand for conducting the reaction as a solution polymerization in anonoxidizing atmosphere effected by nitrogen purging. The reaction isheated to a temperature of around 70° to 85° C. for a time around 1.5 to3 hours. The resultant aqueous solution of the addition interpolymer isuseful directly for coating inorganic surfaces and especially forcoating glass and most particularly glass fibers. With the use of theSSS ionic monomer some of the interpolymer formed can have mer groupingshaving the formula: ##STR4## where p and q are integers as previouslydescribed. With the use of the cationic methacrylate monomer theinterpolymer formed has a majority of mer groupings having the formula:##STR5## wherein:

R is an alkyl group like CH₃ or one with more carbon atoms,

R' is an alkyl group with 1 to around 6 carbon atoms; and

R" is hydrogen and/or an alkyl with 1 to 4 carbon atoms.

Molecular weights of the sodium styrene sulfonate-containinginterpolymer, that is a copolymer, can be around 29,000 number averagemolecular weight and around 350,000 weight average molecular weight. Forthe quaternary ammonium salt-containing interpolymer the number averagemolecular weight can be around 60,000, and the weight average can bearound 155,000.

ILLUSTRATIVE EXAMPLES A

Sodium styrene sulfonate (SSS) in an amount of 150 grams was dissolvedwith water to a one kilogram total in a two liter flask. An amount of0.37 grams potassium persulfate (K₂ S₂ O₈) was added, and the componentswere heated to 72 degrees C. for one hour and fifteen minutes withstirring. The heating was stopped and the heat source removed. A clearpale yellow dried film was produced which was brittle and flaky andwater soluble. The film didn't adhere to a glass slide.

B

Two grams of SSS were dissolved in 20 milliliters of distilled water and0.02 of a gram of potassium persulfate was added. The solution washeated to 60 degrees Celsius for one hour. The product was a viscoussolution that gave a brittle and flaky film. To this latter solutionpartially hydrolyzed gamma-methacryloxypropyltrimethoxy silane or3-(trimethoxysilyl)-propyl methacrylate (A-174 silane) in water wasadded, and the solution was reheated. A film of this solution on a glassslide gave no improvement in adhesion to glass. To the solution with theSSS and A-174 silane some potassium persulfate was added, and thesolution was heated to 60 degrees Celsius. A film of this lattersolution on a glass slide did not give any improvement in adhesion toglass.

C

Sixteen grams of a quaternized product of dimethylaminoethylmethacrylate and methyl chloride were added to twelve grams of water. Anamount of 0.12 of a gram of potassium persulfate (K₂ S₂ O₄) was added,and the components heated at 70 to 80 degrees C. for three hours under anitrogen atmosphere. A dried film of the resultant product was colorlessand did not soften upon standing, and did not adhere to a glass slideand was water soluble.

EXAMPLES EXAMPLE 1

An amount of 475 grams of sodium styrene sulfonate (SSS) as a freeflowing white powder was dissolved in 2000 grams of distilled water. Anamount of 25 grams of (A-174) was added to the solution. Potassiumpersulfate (K₂ S₂ O₈) in an amount of one gram was added to the solutionin the glass reaction vessel. The solution was heated to 80 degreesCelsius with nitrogen bubbled through the solution. After two hours ayellow gelatinous material was evident in the vessel. This material wasnot stirable, but when it was diluted to five (5) percent solids the gelreverted to a solution. The solution was further diluted to 1.25% solidsand applied to glass fibers during their formation. The fibers had afiber diameter of "K"(around 13 micrometers), and four hundred of thefibers were formed into a strand of K-37 construction. The strand waswound on a winder into a annular multilayered package. The strand wastested for the amount of organic coating on the fibers by a loss onignition (LOI) test. The result was an average LOI of 0.44 weightpercent.

EXAMPLE 2

An amount of 147 grams of SSS was charged to a two liter round bottomglass flask, and distilled water was added to 900 grams. Stirring wasbegun and hydrolyzed A-174 silane in acetone was added. This silanesolution was prepared with three grams A-174 silane and acetone to 100grams. To the silane and SSS solution, an amount of 0.37 grams ofpotassium persulfate was added. The solution was heated for 3.45 hoursat 63 degrees C. for around 2.25 hours and at 71 degrees for one hourand at 85 degrees for 0.5 hour. A glass slide was dipped into theresulting solution, and a dried film of the solution on the slideadhered to the glass and was insoluble in water.

EXAMPLE 3

To a three liter glass flask equipped with a stirrer, nitrogen bubblerand thermometer, there was combined 412 grams of SSS, which has amolecular weight of 206 grams, and 1460 grams of distilled water and0.41 grams of Na₂ S₂ O₈. The nitrogen purge was begun, and heat to amaximum temperature of 50 degrees C. was applied to solubilize the SSS.Upon and increase in viscosity a hydrolyzed solution of A-174 silane wasquickly added. The silane solution was prepared by combining 9.96 gramsof A-174 silane with 200 grams of distilled water and adding acetic acidin sufficient quantities to achieve a pH of 5. Also added was a solutionof potassium persulfate that was prepared by combining 0.54 grams with20 grams of distilled water. This mixture was heated to 70 degrees C.for 1.5 hours. An amount of 10 milliliters of isopropyl alcohol wasadded and heating was continued for another 30 minutes. After this timethe temperature was dropped to 65 degrees and the solution was pouredinto a plastic bottle.

EXAMPLE 4

An amount of 30.4 grams of Sipomer Q-6-75 cationic methacrylate monomeras a 75% active water solution was combined with 1.5 grams of A-174silane and with 0.12 of a gram of K₂ S₂ O₈ and 120 grams of distilledwater. The mixture was heated at a temperature in the range of 70 to 80degrees for three hours. A film of the resultant solution was producedwhich softened upon standing, which indicated hydroscopicity.

EXAMPLE 5

The neat 75% active Sipomer monomer was added to distilled water andcombined with 5% A-174 silane and the combination with stirring washeated at a temperature in the range of 80 to 90 degrees C. Eventually aclear solution was obtained. A film of the solution was formed on aglass slide, and the film was water insoluble. This same reaction wasconducted in the presence of potassium persulfate, and no difference inviscosity or other differences were noticed.

EXAMPLE 6

An amount of 100 grams of the Sipomer monomer was combined with twograms of the A-174 silane and 0.1 gram of potassium persulfate and 900grams of distilled water. The combination was heated and stirred undernitrogen purge at 80 degrees C. for four hours. An orange slimy viscoussolution was obtained. A film of the solution formed on a glass slidewas dried, and the resultant film was brittle, but it did not wash offthe slide with water.

EXAMPLE 7

An amount of 692 grams of Sipomer monomer (75 percent active) havingmolecular weight of 207.6 was diluted with distilled water in an amountof 1708 grams and an amount of Na₂ S₂ O₈ of 0.52 grams. This wasachieved in a 3 liter flask. Subsequently, nitrogen purging wascommenced and hydrolyzed A-174 silane was charged to the flask. Thehydrolyzed A-174 silane was prepared by 12.4 grams of A-174 mixed with250 milliliters of acidic acid to achieve a pH in the range of 4 to 5.Heating was started and subsequent thereto, the potassium persulfate inthe amount of 0.68 grams dissolved in 25 grams of water was added. Theheating was up to 40° C. in 10 minutes and up to 55° C. in an additional30 minutes and up to 70° C. in additional 19 minutes and up to 85° C. inan additional 41 minutes and down to 80° C. in an additional 30 minutesto give a total heating time of 2 hours and 20 minutes. After this timethe variac was turned off and 10 grams of isopropyl alcohol was addedand the flask was removed from the mantle and the solution poured into aplastic bottle.

EXAMPLE 8

An amount of 150 grams of 2-acrylamido-2-methylpropane sulfonic acid(AMPS monomer) having a molecular weight of 229 in a 50 percent aqueoussolution was combined with hydrolyzed A-174 silane and 200 millilitersof water. The hydrolyzed silane was prepared from 1.62 grams of thematerial having a molecular weight of 249 added to water (50 ml) whichwas acidified with acidic acid to a pH of 5.0. The mixture in thereaction vessel was stirred until homogeneous. With the addition of theAMPS monomer and water, the solution was purged with nitrogen for 0.5 toone hour and warmed to 40° C. An amount of 0.15 grams of potassiumpersulfate having a molecular weight of 270 was added along with sodiummetabisulfite (0.6 grams). The mixture was warmed to a temperature inthe range of 55° to 60° C. for 2 to 2.5 hours. After this time a glassslide was dipped in the solution to produce a film on the slide and thefilm cured to a colorless film on heating the slide on a hot plate.

EXAMPLE 9

To a 500 ml three-necked, round-bottom glass vessel equipped with athermometer, condenser, nitrogen dispersion tube and addition funnelthere was added 27.8 grams of a sodium hydroxide as a 50 percent aqueoussolution along with 100 ml of water. Methacrylate in an amount of 29.8grams and 50 ml of water was added slowly to the vessel. An amount of 75grams of AMPS 2405 monomer (50 percent solution) and 100 ml of waterwere added to the reaction vessel and nitrogen purging was continued foranother 0.5 hours. Campden sodium metabisulfite (0.4 grams) andpotassium persulfate were dissolved in 4 ml of water and added viasyringe at a temperature of 34° C. to the reaction vessel. An amount of2.53 grams of A-174 silane was hydrolyzed with acidic acid in water andwas slowly added dropwise over a period of time when the temperaturereached 35°-36° C. The mixture became hazy (white) within 0.5 hours;approximately half of the silane was added.

EXAMPLE 10

The A-174 silane in an amount of 2.53 grams, where the molecular weightis 249, was hydrolyzed in 50 ml of distilled water acidified with acidicacid to a pH of 5. A similar reaction vessel to that of Example 9 wascharged with 200 ml of distilled water and 67.6 grams of SSS and 75grams of AMPS 2405 (50 percent aqueous) and another addition ofdistilled water in an amount of 100 ml. The hydrolyzed A-174 silane wasadded and the mixture was warmed to 35° to 40° C. with nitrogen purgingfor one hour. An amount of potassium persulfate of 0.4 grams was mixedwith metabisulfite and added to the mixture of AMPS andpolystyrenesulfonate.

From the aforepresented, an improvement is shown in the affiliation ofthe addition interpolymer to a glass surface versus no affiliation ofthe polymers of Illustrative Examples A, B and C to a glass surface.Although not all of the addition interpolymers of the examples formedideal films, generally the affiliation with the glass surface was betterthan the polymers formed from Illustrative Examples A, B and C.

We claim:
 1. A dried residue upon an inorganic oxide surface having anaddition polymeric reaction product comprising:a. at least oneethylenically unsaturated monomer having an ionic moiety selected fromthe group consisting of sulfonates and quaternary ammonium salts thatmakes the monomer water emulsifiable in an effective amount to give anamount of the reacted monomer in the polymer for at least waterdispersibility of the polymer, b. a copolymerizable organo-functionalsilane compound having ethylenic unsaturation for copolymerization inthe organo-functional group and having associated with the silane threegroups selected from alkoxy, hydroxy, and mixtures thereof, where thesilane compound is present in an effective amount to give an amount offree-radically reacted or pendant silane in the range of about 1 toabout 15 weight percent of the interpolymer, where the addition polymeris formed in the presence of a free-radical initiation catalyst in aneffective catalytic amount and of at least one liquid carrier at anelevated temperature in a nonoxidizing atmosphere, wherein the additionpolymer has pendant ionic moieties and pendant silane moieties, wherethe silane moieties have groups selected from the group consisting ofhydrolyzable, hydrolyzed and partially hydrolyzed groups.
 2. The driedresidue upon an inorganic oxide surface of claim 1, wherein the silanecompound for the addition polymeric reaction product is present in awater soluble organic solvent.
 3. The dried residue upon an inorganicoxide surface of claim 1, wherein the silane compound for the additionpolymeric reaction product is selected from the group consisting ofacrylatoalkoxysilanes, methacrylatoalkoxysilanes, andvinylalkoxysilanes.
 4. The dried residue upon an inorganic oxide surfaceof claim 1, wherein the silane compound for the addition polymericreaction product is partially hydrolyzed.
 5. The dried residue upon aninorganic oxide surface of claim 1, wherein the silane is in a solutionof diluted acetic acid for partial hydrolyzation.
 6. The dried residueupon an inorganic oxide surface of claim 1, wherein the additionpolymeric reaction product is formed with at least one additionalmonomer having ethylenic unsaturation present in an amount of less thanabout 700 weight percent of the polymer.
 7. The dried residue upon aninorganic oxide surface of claim 1, wherein the addition polymericreaction product in the residue has the vinyl monomer selected from thegroup consisting of: acrylic and methacrylic acid, styrene and methylstyrene.
 8. The dried residue upon an inorganic oxide surface of claim1, wherein the addition polymeric product has the ethylenicallyunsaturated monomer with an ionic moiety selected from the groupconsisting of: sodium styrene sulfonate, quaternization product ofdimethylaminoethyl methacrylate and of methyl chloride, quaternizationproduct of vinylpyridinium compound and of (dimethylamino)ethylmethacrylate, and 2-acrylamide-2-methylpropanesulfonic acid, andmixtures of any and all of these.
 9. The dried residue upon an inorganicoxide surface of claim 1, wherein the addition polymeric product haswater as the liquid carrier and the polymerization is solutionpolymerization.
 10. The dried residue upon an inorganic oxide surface ofclaim 1, wherein in the addition polymeric product the amount of thefree-radically reacted and pendant silane is in the range of less thanaround 5 weight percent of the polymer.
 11. The dried residue upon aninorganic oxide surface of claim 1, wherein the inorganic oxide surfaceis glass fiber.
 12. A dried residue upon an inorganic oxide surface,wherein the residue has an addition polymeric reaction product,comprising:a. at least one ethylenically unsaturated monomer having atleast one ionic moiety per monomer and where the ionic moiety isselected from the group consisting of: sulfonates and quaternaryammonium salts and mixtures thereof in an amount to produce thepolymerized reaction product in the polymer in an amount of up to 99weight percent of the polymer; and b. a copolymerizable organofunctionalsilane compound selected from the group consisting ofacrylatoorganoalkoxysilanes, methacrylatoorganoalkoxysilane, andvinylorganoalkoxysilanes where the alkoxy group has alkyl groups with upto five carbon atoms or partial or fully hydrolyzed derivatives in anamount in the range of about 1 to about 15 weight percent of thepolymer; and where the addition polymeric product is formed in thepresence of a water miscible free-radical initiation catalyst in aneffective catalytic amount and in the presence of water in at least aneffective dispersing amount and at an elevated temperature in the rangeof about 80° C. to about 90° C. for a period of time at least toapproach complete polymerization, wherein the addition polymer haspendant ionic moieties and pendant silane moieties that have groupsselected from the group consisting of hydrolyzable, hydrolyzed andpartially hydrolyzed groups.
 13. The dried residue upon an inorganicoxide surface of claim 12, wherein the addition polymeric reactionproduct in the residue has the amount of ethylenically unsaturatedmonomer having at least one ionic moiety in an amount to achieve anamount of reaction monomer in the polymer in the range of about 85 toabout 95 weight percent and the amount of copolymerizable ethylenicallyunsaturated organosilane is effective to achieve an amount of silanewith reactable groups of up to 5 weight percent.
 14. The dried residueupon an inorganic oxide surface of claim 12, wherein the additionpolymeric reaction product in the residue has at least one additionalrepeating unit from an ethylenically unsaturated monomer where theamount of the mer is present in the amount of less than around 70 weightpercent of the polymer and the amount of ethylenically unsaturatedmonomer with the ionic moiety effective to achieve an amount of about 10to about 98 weight percent of the polymer.
 15. The dried residue upon aninorganic oxide surface of claim 12, wherein the inorganic oxide surfaceis glass fiber.
 16. A dried residue upon an inorganic oxide surface,wherein the residue has an addition polymeric product having theformula: ##STR6## wherein: R is hydrogen or an alkyl group,R' isselected from an organic moiety that in addition to the ##STR7## moietyand ionic moiety comprise the ethylenically unsaturated monomer havingan ionic moiety before addition polymerization, R" is hydrogen or analkyl group having one to 5 carbon atoms, R''' is a (C(O)--O--(CH₂)_(x))moiety or (CH₂)_(x) moiety where x is an integer from 1 to 6; and R^(IV)is hydrogen, an alkyl group having 1 to about 4 carbon atoms or amixture thereof, and p and q are integers with values of around 80 toaround 90 for p and of around 1 to around 20 for q.
 17. The driedresidue upon an inorganic oxide surface of claim 16, wherein theaddition polymeric reaction product in the residue has at least oneaddition repeating unit from an ethylenically unsaturated monomer wherethe amount of the mer is present in the amount of less than around 70weight percent of the polymer and the amount of ethylenicallyunsaturated monomer with the ionic moiety effectively to achieve anamount of about 10 to about 98 weight percent of the polymer.
 18. Thedried residue upon an inorganic oxide surface of claim 16, wherein theinorganic oxide surface is glass fiber.
 19. A dried residue upon aninorganic oxide surface, wherein the residue has an additionpolymerization product having the formula: ##STR8## wherein: R is analkyl group like CH₃ or an alkyl group with more carbon atoms,R' is analkyl group with 1 to around 6 carbon atoms; and R" is hydrogen and/oran alkyl with 1 to 4 carbon atoms and p and q are integers with valuesof around 80 to around 90 for p and around 1 to around 20 for q.
 20. Thedried residue upon an inorganic oxide surface of claim 19, wherein theaddition polymeric reaction product in the residue has at least oneadditional repeating unit from an ethylenically unsaturated monomerwhere the amount of the mer is present in the amount of less than around70 weight percent of the polymer and the amount of ethylenicallyunsaturated monomer with the ionic moiety effectively to achieve anamount of about 10 to about 98 weight percent of the polymer.
 21. Thedried residue upon an inorganic oxide surface of claim 19, wherein theinorganic oxide surface is glass fiber.
 22. A dried residue upon aninorganic oxide surface, wherein the residue has an additionpolymerization product having the formula: ##STR9## wherein R ishydrogen or alkyl group having one to four carbon groups or a mixturethereof, and p and q are integers where p has a value in the range ofaround 80 to around 99 and where q has a value in the range of 1 toaround
 20. 23. The dried residue upon an inorganic oxide surface ofclaim 22, wherein the addition polymeric reaction product in the residuehas at least one additional repeating unit from an ethylenicallyunsaturated monomer where the amount of the mer is present in the amountof less than around 70 weight percent of the polymer and the amount ofethylenically unsaturated monomer with the ionic moiety effectively toachieve an amount of about 10 to about 98 weight percent of the polymer.24. The dried residue upon an inorganic oxide surface of claim 22,wherein the inorganic oxide surface is glass fiber.